4'-(4-硝基苯基)-2,2':6',2''-三联吡啶 | 129077-51-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 中文名称: 4'-(4-硝基苯基)-2,2':6',2''-三联吡啶
• 中文别名: 4'-（4-硝基苯基）-2,2':6',2''-三联吡啶
• 英文名称: 4'-(4-nitrophenyl)-2,2':6',2''-terpyridine
• 英文别名: 4'-(p-nitrophenyl)-2,2':6',2''-terpyridine；4'-(4-nitrophenyl)-2,2':6',2"-terpyridine；4′-(4-nitrophenyl)-2,2′:6′,2″-terpyridine；4-(4-nitrophenyl)-2,6-dipyridin-2-ylpyridine
• CAS: 129077-51-6
• 化学式: C₂₁H₁₄N₄O₂
• 分子量: 354.368
• InChiKey: SLAKPUZCHMXDSL-UHFFFAOYSA-N

物化性质

• 熔点：
  158-159 °C(Solv: ethanol (64-17-5))
• 沸点：
  536.1±45.0 °C(Predicted)
• 密度：
  1.280±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  84.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4'-(4-硝基苯基)-2,2':6',2''-三联吡啶 以 N,N-二甲基乙酰胺 为溶剂， 生成 [Ir(4-ethylbenzoate)3(4'-(phenyl-p-nitro)-2,2':6',2''-terpyridine)]
  参考文献：
  名称：

  Terpyridine Zn(II), Ru(III), and Ir(III) Complexes:  The Relevant Role of the Nature of the Metal Ion and of the Ancillary Ligands on the Second-Order Nonlinear Response of Terpyridines Carrying Electron Donor or Electron Acceptor Groups

  摘要：

  Coordination of 4 '-(C6H4-p-X)-2,2 ':6 ',2 ''-terpyridines [X = NO2, NBu2, (E)-CH=CH-C6H4-p-NBu2, (E,E)-(CH=CH)(2)C6H4-p-NMe2] to Zn(II), Ru(III), and Ir(III) metal centers induces a significant enhancement of the absolute value of the second-order nonlinear optical (NLO) response of the terpyridine, measured by means of both electric field induced second harmonic generation and solvatochromic methods. By varying the nature of the metal center, the enhanced second-order NLO response shifts from positive to negative. Such a shift is controlled by electronic charge-transfer transitions, such as metal-to-ligand or ligand-to-metal transitions, in addition to the intraligand charge transfer. The enhancement generated by coordination is also controlled by the chelation effect and by fine-tuning of the ancillary ligands.

  DOI：

  10.1021/ic050975q
• 作为产物：
  描述：

  2-乙酰基吡啶 在 ammonium acetate 、 sodium hydroxide 作用下， 以 甲醇 为溶剂， 反应 4.0h， 生成 4'-(4-硝基苯基)-2,2':6',2''-三联吡啶
  参考文献：
  名称：

  聚集诱导发射（AIE）活性4-氨基-1,8-萘二甲酰亚胺-特雷格氏碱，用于选择性感应竞争性水性介质中的化学炸药。

  摘要：

  合成了4-氨基-1,8-萘二甲酰亚胺-Tröger的碱性荧光团TBNap-TPy，并装饰了苯基-吡啶基部分，并对其聚集诱导发射（AIE）行为进行了评估。TBNap-TPy进一步用作区分π电子缺陷型硝基芳香族化合物的荧光传感器。TBNap-TPy具有最大的荧光猝灭性，对苦味酸具有高选择性，苦味酸是在染料行业中广泛使用的有害环境污染物。

  DOI：

  10.1039/c9cc08457f

文献信息

• The synthesis of 4′-aryl substituted terpyridines by Suzuki cross-coupling reactions: substituent effects on ligand fluorescence
  作者：Wendy Goodall、Kerstin Wild、Kathryn J. Arm、J. A. Gareth Williams

  DOI：10.1039/b205330f

  日期：——

  Several 4′-aryl-substituted 2,2′:6′,2″-terpyridines (tpy-C6H4R) have been prepared by palladium-catalysed cross-coupling of 4′-bromoterpyridine or 4′-triflate-terpyridine (triflate = trifluoromethylsulfonyloxy) with aryl boronic acids or esters, RC6H4B(OR′)2 (R = H, m-NH2, p-CHO, -NO2, -CN, -NMe2, -NPh2). The new ligand 4′-mesitylterpyridine (mesityl = 2,4,6-trimethylphenyl) was prepared in the same way. Similarly, 4′-bromophenylterpyridine (tpy-ϕ-Br) has been cross-coupled with aryl halides to generate several new biaryl-substituted terpyridines (tpy-ϕ-C6H4R where R = H, p-CN, NMe2, NPh2), together with two related compounds with pendent 3- or 4-pyridyl groups (tpy-ϕ-C6H4-py). For selected compounds, the alternative coupling strategy of reaction of a terpyridine-4-boronate or terpyridine-4-phenylboronate with the appropriate aryl halide has also been investigated (e.g. to prepare tpy-ϕ-C6H4NO2), but was generally found to be less satisfactory. All of the compounds are fluorescent in the UV region of the spectrum, the biaryl-substituted compounds being only slightly red-shifted compared to the monoaryl systems, but with the further red-shift that accompanies protonation being more significant for the former. Fluorescence lifetimes in solution are in the range 1–5 ns. The emission spectra of the aminobiphenyl-substituted compounds (tpy-ϕ-C6H4NR″2, where R″ = Me or Ph) display a large red-shift with increasing solvent polarity, suggesting the involvement of an intramolecular charge transfer state, as found previously for the two analogues omitting the phenyl ring (tpy-C6H4NR″2). In contrast to the latter, however, protonation or binding of a Lewis acidic metal ion to the aminobiphenyl compounds serves to quench almost completely their emission.

  通过钯催化的交叉偶联反应，制备了几种4′-芳基取代的2,2′:6′,2″-三联吡啶（tpy-C6H4R），涉及4′-溴三联吡啶或4′-三氟甲磺酸酯三联吡啶（triflate = 三氟甲磺酰氧基）与芳基硼酸或硼酸酯的反应，RC6H4B(OR′)2（R = H, m-NH2, p-CHO, -NO2, -CN, -NMe2, -NPh2）。新配体4′-三甲基苯基三联吡啶（mesityl = 2,4,6-三甲基苯基）也通过相同方法制备。类似地，4′-溴苯基三联吡啶（tpy-Φ-Br）已与芳基卤化物交叉偶联，生成了几种新的双芳基取代三联吡啶（tpy-Φ-C6H4R，其中R = H, p-CN, NMe2, NPh2），以及两种含有3-或4-吡啶基侧链的相关化合物（tpy-Φ-C6H4-py）。对于选定的化合物，还研究了替代的偶联策略，即反应一个三联吡啶-4-硼酸酯或三联吡啶-4-苯基硼酸酯与适当的芳基卤化物（例如制备tpy-Φ-C6H4NO2），但通常发现效果较差。所有化合物在紫外区域都有荧光发射，双芳基取代的化合物相比于单芳基系统仅有轻微的红移，但其伴随质子化产生的进一步红移对前者更为显著。溶液中的荧光寿命在1~5纳秒范围内。氨基联苯取代化合物的发射光谱（tpy-Φ-C6H4NR″2，其中R″ = Me或Ph）随着溶剂极性的增加显示出较大的红移，表明存在分子内电荷转移态，这与先前报道的两种省略苯环的类似物（tpy-C6H4NR″2）一致。然而，与后者不同，氨基联苯化合物在质子化或与路易斯酸性金属离子结合时，其发射几乎完全淬灭。
• Phenyl-substituted 2,2′:6′,2″-terpyridine as a new series of fluorescent compounds—their photophysical properties and fluorescence tuning
  作者：Toshiki Mutai、Jin-Dong Cheon、Shinpei Arita、Koji Araki

  DOI：10.1039/b102685m

  日期：——

  Several phenyl-substituted 2,2′:6′,2″-terpyridines (tpy) were synthesized and it was found that 4′-phenyl tpy (ptp, 3) exhibited the most effective fluorescence, whose quantum yield was up to 0.64 in cyclohexane. For further study on tuning the fluorescence properties of ptp, different substituents were introduced into the p-position of the phenyl group. While Br- 10, Cl- 11, and CH3-ptp 12 showed their absorption and fluorescence in the same region as 3, those of NH2- 14 and Me2N-ptp 15 were observed at much longer wavelengths. In addition, fluorescence maxima of 14 and 15 showed large (>130 nm) solvent dependence. The difference between ground and excited state dipole moment (Δμ) for 15 was estimated to be 15.2 D by the Lippert–Mataga equation, indicating the intramolecular charge transfer (ICT) process. Semi-empirical MO calculation (MOPAC/AM1) demonstrated that the HOMO-1, HOMO and LUMO of 3, 10–12 were mainly localized on the phenyl (πph), tpy (πtpy) and tpy (π*tpy) part, respectively, indicating that the lowest energy absorption band of 3, 10–12 was the local excitation (πtpy–π*tpy). In the case of 14 and 15, which have an electron-donating substituent, πph instead of πtpy became the HOMO. Thus, the lowest energy absorption of 14 and 15 was an ICT transition (πph–π*tpy), and a large red shift of the fluorescence occurred. In these compounds, the energy level of πph is controlled without affecting that of πtpy and π*tpy, suggesting a novel approach for tuning the color of fluorescence.

  合成了几种苯基取代的2,2':6',2''-三联吡啶（tpy），发现4'-苯基tpy（ptp，3）具有最有效的荧光，其在环己烷中的量子产率高达0.64。为了进一步研究调节ptp的荧光性质，将不同的取代基引入苯环的p位。Br-10，Cl-11和CH3-ptp 12显示与3相同的吸收和荧光区域，而NH2-14和Me2N-ptp 15的吸收和荧光则在更长的波长处被观察到。此外，14和15的荧光最大值显示了大于130 nm的溶剂依赖性。根据Lippert-Mataga方程，15的基态和激发态偶极矩差（Δμ）估计为15.2 D，表明存在分子内电荷转移（ICT）过程。半经验MO计算（MOPAC/AM1）表明，3、10-12的HOMO-1、HOMO和LUMO主要分别定域在苯基（πph）、tpy（πtpy）和tpy（π*tpy）部分，表明3、10-12的最低能量吸收带是局部激发（πtpy-π*tpy）。对于具有电子给体取代基的14和15，πph而非πtpy成为HOMO。因此，14和15的最低能量吸收是ICT跃迁（πph-π*tpy），并发生了大幅度的荧光红移。在这些化合物中，πph的能级可以在不影响πtpy和π*tpy能级的情况下进行调控，这为调节荧光颜色提供了一种新方法。
• Optimising the synthesis, polymer membrane encapsulation and photoreduction performance of Ru(ii)- and Ir(iii)-bis(terpyridine) cytochrome c bioconjugates
  作者：David Hvasanov、Alexander F. Mason、Daniel C. Goldstein、Mohan Bhadbhade、Pall Thordarson

  DOI：10.1039/c3ob40620b

  日期：——

  Ruthenium(II) and iridium(III) bis(terpyridine) complexes were prepared with maleimide functionalities in order to site-specifically modify yeast iso-1 cytochrome c possessing a single cysteine residue available for modification (CYS102). Single X-ray crystal structures were solved for aniline and maleimide Ru(II) 3 and Ru(II) 4, respectively, providing detailed structural detail of the complexes. Light-activated bioconjugates prepared from Ru(II) 4 in the presence of tris(2-carboxyethyl)-phosphine (TCEP) significantly improved yields from 6% to 27%. Photoinduced electron transfer studies of Ru(II)–cyt c in bulk solution and polymer membrane encapsulated specimens were performed using EDTA as a sacrificial electron donor. It was found that membrane encapsulation of Ru(II)–cyt c in PS140-b-PAA48 resulted in a quantum efficiency of 1.1 ± 0.3 × 10−3, which was a two-fold increase relative to the bulk. Moreover, Ir(III)–cyt c bioconjugates showed a quantum efficiency of 3.8 ± 1.9 × 10−1, equivalent to a ∼640-fold increase relative to bulk Ru(II)–cyt c.

  制备了含有马来酰亚胺功能的钌(II)和铱(III)双三吡啶配合物，以便在酵母同源1细胞色素c上，针对可用于修饰的单个半胱氨酸残基（CYS102）进行位点特异性修饰。分别解析了苯胺和马来酰亚胺钌(II) 3和钌(II) 4的单晶X射线晶体结构，提供了这些配合物的详细结构细节。在三(2-羧乙基)膦(TCEP)存在下，从钌(II) 4制备的光活化生物偶联物显著提高了产量，从6%增加到27%。在大量溶液和聚合物膜封装的样品中，使用EDTA作为牺牲电子供体，进行了钌(II)–细胞色素c的光诱导电子转移研究。发现将钌(II)–细胞色素c封装在PS140-b-PAA48膜中，量子效率为1.1 ± 0.3 × 10^−3，相对于大量溶液中的封装效率增加了两倍。此外，铱(III)–细胞色素c生物偶联物的量子效率为3.8 ± 1.9 × 10^−1，相当于相对于大量溶液中的钌(II)–细胞色素c提高了约640倍。
• Development of Luminescent Europium(III) and Terbium(III) chelates of 2,2′:6′,2″- terpyridine derivatives for protein labelling
  作者：Veli-Matti Mukkala、Matti Helenius、Ilka Hemmilä、Jouko Kankare、Harri Takalo

  DOI：10.1002/hlca.19930760323

  日期：1993.5.12

  The synthesis and luminescence properties are reported for 20 different chelates composed of 2,2′:6′,2″-terpyridine as the energy-absorbing and donating group, EuIIIand TbIII as the emitting ions, methylenenitrilo(acetic acids) as the stabel chelate-forming moieties, and isothiocyanato or(4,6-dichloro-1,3,5-triazin-2-yl)amino groups as the activated moieties for coupling to biomolecules.

  报告了20种不同螯合物的合成和发光性能，这些螯合物由2,2'：6'，2''-三联吡啶作为能量吸收和供电基团，Eu III和Tb III作为发射离子，亚甲基三乙酸（乙酸）作为稳定的形成螯合物的部分，以及异硫氰酸根合或（4,6-二氯-1,3,5-三嗪-2-基）氨基作为与生物分子偶联的活化部分。
• Surface Bottom-up Fabrication of Porphyrin-terminated Metal Complex Molecular Wires with Photo-electron Conversion Properties on ITO
  作者：Mariko Miyachi、Makiko Ohta、Misaki Nakai、Yoshihiro Kubota、Yoshinori Yamanoi、Tetsu Yonezawa、Hiroshi Nishihara

  DOI：10.1246/cl.2008.404

  日期：2008.4.5

  We fabricated photoelectron conversion system with porphyrin-terminated “molecular wires” on an ITO surface synthesized using stepwise metal–terpyridine complexation reactions. The efficiency and the electrode potential singnificantly depended on the metal center of the bis(terpyridine) complex unit in the molecular wire.

  我们在采用分步金属–吡啶复合反应合成的ITO表面上制造了具有卟啉末端的“分子电线”的光电子转换系统。效率和电极电位显著依赖于分子电线中双（吡啶）复合单元的金属中心。